Metallizable polyazo dyestuffs



Patented Nov. 23, 1948 w UNITED STATES PATENT OFFICE METALLIZ-ABLE POLYAZO DYESTUFFS Walter Wehrli and Charles Pe'ti'tjean, Basel,

-Switzerland, assignors to Sandoz Limited, Basel, Swtzerland No Drawing. Application April 1946, Serial No. 661,863. In Switzerland April 16, 1945 6 Claims. (01. 260-1661 '1 2 The present invention relates to new metalliz-- wherein A and Z have the above meanings, can aisle polyazo dyestuffs. be produced in different ways. Thus it "is pos- It has been found that valuable metallizable sible to couple for instance diazo compounds, polya-zo dyestuffs can be obtained by causing l which may contain azo groups, but no .free amino mole of resorcinal to react in any order of sue 5 groups, no acylated amino groups and no carbon session, on the one with 1 mole of a diaatoms capable of coupling, with l-hydroxy-Z- zotized aminazo dyestuff of the general formula aminobenzene acylated in the amino group and containing no substituents in 4-position or with AN=N Z derivatives thereof. By saponifying the acidamino group present in the coupling product the .NH? desired lam inoazo dyestuffs are produced. wherein A represents the radical of a diazo or on the other hand-1 it is also possible to coupling component, which radical may contain (111% aminoazo dyestufis corresponding n t ldiazfltisalble m group's nor carbon above mentioned general constitution by couatgmg which ar w m f Coupling but may pling .1.--diazo-3-acylaminoA-hydroxybenzenes or wma' ago groupsfione hydroxylgmup in derivatives thereof with coupling components tion to th amino grou :being ,present, in w containing only one single grouping enabling the benzene radical -Z in any event and the benzene coupling, but containing free acylated'amino radical Z being capable of containing still further groups and by s tl Saponifymg the inter" :sulostituents, and, on the other hand, with 1 mole mediate pToductssoobtamed- Of a ldiazo ompound 1 the :genena l formula The obtainable according to Dre a sent invention 'dy'e cotton 'as well as regenerated cellulose in brown shades. By an after-treatment of the dyeings with metal-yielding agents the dye- I ings will be improved with respect to their wherein X represehtse one of the groupings fastness properties. Thus it is possible to con- --l l-I-I.CO and CO.NH, R. represents the siderably increase the light-fastness as Well as radical ofan o-hydroxycarboxylie acid of the and the fastness proper-ties in the moist state by an series and Y stands for a diazo group, the nuclei aiter-treatment oi the dyeings with copper-yield- C and D being capable of containing still further ing agents.

substituents. The present invention will now be described The same dyestuffs are also obtained by diazo- 'by way of examples, without however being limtizing dyestuffs of the general formula ited thereto. The parts are by weight.

N=N- Egon 1m, I i n wherein A represents the radical *of a diaz'o or Example 1 coupling component, which may contain neither "diazotisable amino "groups nor carbo w 22.3 parts of naphthionic acid are diazotized in capable of coupling, t which may contain 40 the conventional manner and the so-obtained groups, and wherein X stands for one of the diaZO Compound coupled the Presence of grgf pihgs T H w the sodium carbonate with a solution of 15.1 parts o d t t t x l group st b w of 1acetamino-2-hydroxybenzene, 13.3 parts of sentin the benzene radical B in o-position to the c o y a d Wat r- The monoazo azo group I and that Z, c, and D may still conu s p t d by ad iti n f hyd ot'a n further substituents, and by coupling the chloric acid andfiltered. It issaponified byheatproducts Smobtained t .b;hya1 ox afboxy1i ing with dilute sulfuric acid. The saponiflcation acids of the aryl serie product is filtered and washed with water. It

The amino azo dyestufis required for the preppossesses the p e fo mula aration of thenew dyestffsandhavingthe general i 1 formula HOaS N=NOH For the further diazotization of the monoazo dyestufi the same is dissolved in water and caustic soda lye. This solution is treated with a solution of 7 parts of sodium nitrite, the whole being caused to flow, while cooling and vigorously stirring, into hydrochloric acid. When the diazotization is complete, the diazo compound is coupled with a solution of 11 parts of resorcine in the presence of sodium carbonate. The disazo dyestuff is precipated by means of hydrochloric acid and filtered. It is dissolved in a mixture of water and sodium carbonate and coupled with the intermediate product obtainable in the conventional manner from 22.7 parts of 4.4'-diaminobenzanilide and 13.8 parts of salicyclic acid. The tetrakisazo dyestuff is precipitated by means of sodium chloride and filtered off. It constitutes, when dried, a dark powder dyeing cotton and regenerated cellulosic fibres in reddish-brown shades. When after-treated with copper-sulfate,

the dyeings become reddish-brown, the fastness properties thereof to washing, to light, to acid and to alkali being considerably increased.

If, instead of naphthionic acid, 2-naphthyl amine-B-sulfonic acid or l-naphthylamine-G- sulfonic acid is used, dyestuifs of similar shades and fastness properties are obtained.

When using in this example, instead of the intermediate product resulting from 4.4-diaminobenzanilide and salicylic acid, the diazo compound consisting of 37.6 parts of the dyestuif of :74

the formula HOOC there will be obtained a dyestuff of similar fastness properties. It dyes cotton and regenerated cellulosic fibres in yellowish-brown shades which, when after-treated with copper sulfate, become brown.

Example 2 The diazo compound produced in the usual manner from 22.3 parts of naphthionic acid is combined with a solution of 16.5 parts of 1- methyl 3 acetamino 4 hydroxybenzene, 13.3 parts of caustic soda lye and with water in the presence of sodium carbonate. The monoazo dyestufi is precipitated with sodium chloride and saponified by heating the mixture for several hours with dilute sulfuric acid. After cooling the monoazo dyestuff of the probable formula 6H NH:

is filtered olf and Washed'with water, It is dissolved in water and caustic soda lye, then treated with '7 parts of sodium nitrite and allowed to drop while stirring thoroughly at a low temperature into hydrochloric acid. After completion of the diazotization the diazo compound is coupled with a soda alkaline solution containing 11 parts of resorcine. The diazo dyestuff is precipitated by addition of hydrochloric acid. It is dissolved in a mixture of water and sodium carbonate and coupled with the intermediate compound produced in the usual manner from 22.7 parts of 4.4- diaminobenzanilide and 13.8 parts of salicylic acid. The tetrakisazo dyestuff is precipitated in the heat with sodium chloride, filtered and dried.

It constitutes a dark powder dyeing cotton and regenerated cellulose in yellowish-brown shades.

When after-treated with copper sulfate, the dyeings become dark brown and their fastness properties to washing, to acid and to alkali will considerably be improved.

Example 3 9.3 parts of aniline are diazotized in the usual manner and coupled in the presence of sodium carbonate with a solution of 15.1 parts of l-acetamino-Z-hydroxybenzene, 13.3 parts of 30% caustic soda lye and with water. The monoazo dyestufi is thus precipitated and filtered oiT. It possesses the probable formula ITIHCOCH;

It is saponified by heating with dilute caustic soda lye, precipitated by means of hydrochloric acid and filtered ofi. The dyestuff is then suspended in water, a solution of 7 parts of sodium nitrite being added thereto and the suspension allowed to run into hydrochloric acid, while well stirring. After completion of the diazotization the diazo compound will be coupled with a solution of 11 parts of resorcine and water in the presence of sodium carbonate. The disazo dyestuff is precipitated and filtered off. It is dissolved in water under addition of caustic soda lye and coupled in the presence of sodium carbonate with the intermediate product produced in the usual way by interacting 22.7 parts of 4.4'- diaminobenzanilide and 13.8 parts of salicylic acid. The tetrakisazo dyestuff is precipitated, still warm, by addition of sodium chloride and filtered off. When dried, it is a dark powder which dyes cotton and regenerated cellulosic fibres in yellowish-brown shades. When aftertreated with copper sulfate, the dyeings become brown, while the fastness properties thereof to washing, light and the alkali are substantially increased.

When using, instead of aniline, 12.1 parts of m-xylidine, a tetrakisazo dyestu'ff of similar properties is obtained, this dyestuff dyeing cotton and regenerated cellulose likewise in yellowish shades which are converted into brown shades by an after-treatment with copper salts.

Instead of aniline, also 2-aminotoluene-4-sulfonic acid, 1-aminobenzene-4-sulfonic acid, 1- aminobenzene-3-sulfonic acid or l-aminobenzene-Z-sulfonic acid may be used,whereby dyestufls with similar shades and fastness properties are obtained.

Example 4 18.9 parts of 1-amino-2-hydroxybenzene-5-sulfonic acid are diazotized in the usual manner and coupled in the presence of sodium carbonate with 15.1 parts of 1-acetamino-2-hydroxybenzene, 13.3 parts of 30% caustic soda lye and water. The so-obtained monoazo dyestuff is precipitated by means of sodium chloride. In order to saponify the same it is heated with dilute caustic soda lye, then precipitated by addition of hydrochloric acid and filtered ofi. The dyestufi possesses the probable formula OH NH2 G g S OaNa For further diazotization this dyestuff is suspended in water and, after addition of 7 parts of sodium nitrite, acidified with hydrochloric acid.

After completion of the dlazotization the diazo compound is coupled with a solution of 11 parts of resorcine and of water in the presence of sodium carbonate. The disazo dyestuff is precipitated by means of hydrochloric acid and filtered off. The dyestuff is dissolved in a solution ofwater and sodium carbonate and coupled with the intermediate product produced in the usual way from 22.7 parts of 4.4-diaminobenzanilide and 13.8 parts of salicylic acid. The tetrakisazo dyestufi is precipitated in the heat with sodium chloride, filtered off and dried In this way a dark powder is obtained which dyes cotton and regenerated cellulose in reddish-brown shades, which, when after-treated with copper salts become brown. Simultaneously the fastness properties in the moist state, to light; to acid and to alkali are substantially improved.

If in Example 4 the l-amino-Z-hydroxybenzene-5-sulfonic acid is replaced by 1-amino-2- hydroxy-B-nitrobenzene, there will be obtained a reddish-brown dyestuff, whose dyeings become dark brown on after-coppering the same and possess good fastness properties.

When in this example, instead of the intermediate product from 4.4'-diaminobenzanilide and salicylic acid, the diazo compound obtainable from 37.6 parts of the following dyestuff is used, there will be obtained a dyestuff dyeing cottonand regenerated cellulose in yellowishbrown shades. After-treated with copper sulfate these dyeings will be changed into brown and the fastness properties to washing, light, acid and to alkali are substantially improved.

Example 5 12.3 parts of 4-methoxy-1-aminobenzene are diazotized in a conventional manner and coustuff of the following formula is filtered off, suspended in water, treated with '7 parts of Sodium-nitrite and acidified with hydrochloric acid. After completion of the diazotization the diazo compound is coupled with a solution of 11 parts of resorcine and water in the presence of sodium carbonate. The disazo dyestuif is precipitated by addition of hydrochloric acid, filtered and dissolved in water and sodium carbonate. The resulting solution is coupled with the intermediate product produced in the usual way from 22.7 parts of 4.4'-diaminobenzanilide and 13.8 parts of salicylic acid. The tetralcisazo dyestuff is precipitated in the heat by 'mean's of sodium' chloride, filtered oil and dried. In this way a dark powder is obtained which dyes cotton and regenerated cellulose in yellowish-brown shades which, on after-treatment with copper sulfate, become brown. The fastness properties to light, to acid as well as in the moist state are thus substantially improved.

When using, instead of 4-methoXy-l-aminobenzene, 2 -methoxy-l-aminobenzene 5-sulfonic acid, a dyestuif of similar properties'is obtained.

What we claim is:

1. A metallizable polyazo dyestuff of the formula COOH wherein A stands for a radical free from diazotizable amino groups and containing no carbon atoms cap-able of coupling, this radical being selected from the group consisting of substituted and unsubstituted benzene and naphthalene radicals, the benzene nucleus Z contains one hydroxy group in ortho-pos-ition to the azo group present in position 3, the free positions of the benzene nucleus Z being substituted by a member selected fromthe class consisting of hydrogen and alkyl, and X stands for a member selected from the group consisting of NH.CO and -CO.NH.

2. A metallizable polyazo dyestufl of the formula COOH wherein A stands for a radical free from diazotizable amino groups and containing no carbon atoms capable of coupling, this radical being selected from the group consisting of substituted 7 wherein A stands for a radical free from diazo- 4;'A metallizable polyazo dyestufi of the fortizable amino groups and containing no carbon mula.

V coon OH OH 2 I Hols N=N atoms capable of coupling, this radical being 5. A metallizable polyazo dyestufi of the forselected from the group consisting of substituted mula I l COOH I I OH OH and unsubstituted benzene and naphthalene radi- 6. A metallizable polyazo dyestuff of the for cals and the benzene nucleus Z contains one hymula N 02 droxy group in ortho-position to the azo group WALTER WEHRLI.

present in position 3. CHARLES PETITJEAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name 2 Date Number Name I Date 2,127,678 Delfs et a1 Aug. 23, 1938 2,328,465 Kopp Aug. 31, 1943 2,196,028 Roos Apr. 2, 1940 2,394,114 Siebert Feb. 5,1946 2,226,675 Straub et a1 Dec. 31, 1940 

